Since the advent of rational organic synthesis, practitioners in the field have been refining their craft to target compounds of immense complexity. Synthetic methodologies discovered through these pursuits have provided a fertile ground to expand our understanding of conceptually important ideas (e.g., bonding, aromaticity, solid-state interactions, reaction mechanisms). While intellectually stimulating, the focus of this field has been shifting toward the targeted synthesis of compounds with desirable properties. Our project aligns with this shift and has produced novel molecules of fundamental importance and a foundation toward functional organic materials. Organic chemists continue to uncover synthetic methodology that is perceptively simple to apply to ‘classical’ structures, but many compounds of interest are exceedingly difficult to obtain or have remained elusive. Thus, the preparation of various 2-indanone derivatives provided interesting challenges with surprising outcomes. A small library of aryl-substituted 2-indanones was obtained where individualized synthetic routes were necessary according to the electronic requirements of each system. Through meticulous optimization, reproducible routes were realized to produce multigram quantities of these precursors for the generation and dimerization of their respective isoindenone derivatives.Through this project, we have developed reliable protocols to a series of isoindenone and selected isoindene dimers, both novel scaffolds which may be utilized to study their fleeting-intermediate monomers and construct functional organic materials. The novelty of this scaffold is derived from the offset arene units, demonstrated to direct arene-arene interactions in the solid state – a necessary property for organic semiconductors. The introduction of electron-donating or withdrawing arene substituents provides electronic contrast between these structures while selected derivatives may be amenable to N-heterocyclic rectilinear arene extension.